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Book Details
Abstract
Solid-state NMR covers an enormous range of material types and experimental techniques. Although the basic instrumentation and techniques of solids NMR are readily accessible, there can be significant barriers, even for existing experts, to exploring the bewildering array of more sophisticated techniques. In this unique volume, a range of experts in different areas of modern solid-state NMR explain about their area of expertise, emphasising the “practical aspects” of implementing different techniques, and illustrating what questions can and cannot be addressed. Later chapters address complex materials, showing how different NMR techniques discussed in earlier chapters can be brought together to characterise important materials types. The volume as a whole focusses on topics relevant to the developing field of “NMR crystallography” – the use of solids NMR as a complement to diffraction crystallography.
This book is an ideal complement to existing introductory texts and reviews on solid-state NMR. New researchers wanting to understand new areas of solid-state NMR will find each chapter to be the equivalent to spending time in the laboratory of an internationally leading expert, learning the hints and tips that make the difference between knowing about a technique and being ready to put it into action. With no equivalent on the market, it will be of interest to every solid-state NMR researcher (academic and postgraduate) working in the chemical sciences.
Dr Paul Hodgkinson is a Reader in Magnetic Resonance at Durham University, UK. His research combines interests in technique development and methodology in solid-state NMR as well as applications to chemical problems. Applications of NMR have been in the area of structural chemistry, particularly of pharmaceutical materials and systems with mobility, such as soft solids and solvates. A particular interest is in combining information from diffraction-based experiments, NMR and computation of NMR parameters (using DFT codes), and dynamics (molecular dynamics simulations).
Table of Contents
| Section Title | Page | Action | Price |
|---|---|---|---|
| Cover | Cover | ||
| Preface | v | ||
| Contents | ix | ||
| Methods for Spin-1/2 Nuclei | 1 | ||
| Chapter 1 Heteronuclear Correlation Solid-state NMR Spectroscopy with Indirect Detection under Fast Magic-angle Spinning | 3 | ||
| 1.1 Introduction | 3 | ||
| 1.2 Basic Aspects of Fast MAS | 4 | ||
| 1.2.1 Sensitivity | 5 | ||
| 1.2.2 1H Resolution: Indirect Detection of Lower-γ Nuclei | 5 | ||
| 1.2.3 Flexibility in Using High and Low RF Magnetic Fields | 9 | ||
| 1.3 Hardware Handling | 11 | ||
| 1.3.1 Gas Lines | 11 | ||
| 1.3.2 Probes | 12 | ||
| 1.3.3 MAS Rotors | 13 | ||
| 1.3.4 Magic-angle Adjustment | 15 | ||
| 1.3.5 Frictional Heating | 16 | ||
| 1.3.6 Control of t1-Noise | 17 | ||
| 1.4 Optimization of 1H-Detected 2D HETCOR Experiments | 17 | ||
| 1.4.1 Heteronuclear Dipolar Recoupling by CP and SR421 (HSQC, D-HMQC) | 22 | ||
| 1.4.2 1H–1H Recoupling (HSQC) | 24 | ||
| 1.4.3 1H–1H Homonuclear Decoupling (CP/J-INEPT and J-HMQC) | 25 | ||
| 1.4.4 Excitation and Reconversion Pulse on X Nuclei (HMQC) | 28 | ||
| 1.4.5 J-transfers (CP/J-INEPT and J-HMQC) | 29 | ||
| 1.4.6 Heteronuclear Decoupling (All Experiments) | 30 | ||
| 1.4.7 2D Experiments | 31 | ||
| 1.5 Conclusion | 32 | ||
| Acknowledgements | 33 | ||
| References | 33 | ||
| Chapter 2 High-resolution 1H 2D Magic-angle Spinning Techniques for Organic Solids | 39 | ||
| 2.1 Introduction | 39 | ||
| 2.2 Underlying Concepts | 40 | ||
| 2.2.1 1H and 13C MAS NMR Linewidths | 40 | ||
| 2.2.2 1H Homonuclear Decoupling | 42 | ||
| 2.2.3 Recoupling of Dipolar Couplings Under MAS | 43 | ||
| 2.2.4 Using 1H Spin Diffusion Under MAS: The NOESY Pulse Sequence | 48 | ||
| 2.2.5 Spin-echo Coherence Lifetimes | 48 | ||
| 2.2.6 Set-up: 1H–13C CP MAS NMR of L-Alanine | 49 | ||
| 2.3 Methods and Applications | 50 | ||
| 2.3.1 One-dimensional 1H One-pulse Fast MAS NMR | 50 | ||
| 2.3.2 1H DQ and Spin-diffusion (NOESY) NMR Spectroscopy Under Fast MAS | 53 | ||
| 2.3.3 1H–13C and 14N–1H Heteronuclear Correlation Under Fast MAS | 54 | ||
| 2.3.4 1H DQ CRAMPS NMR Spectroscopy | 58 | ||
| 2.3.5 1H–13C Heteronuclear Correlation NMRSpectroscopy Using Moderate MAS and 1H Homonuclear Decoupling | 63 | ||
| 2.3.6 NMR Crystallography Combining 1H MASNMR Techniques, GIPAW Calculation ofNMR Parameters and Complementary Experimental Methods | 66 | ||
| 2.4 Concluding Remarks | 71 | ||
| Acknowledgements | 72 | ||
| References | 72 | ||
| Chapter 3 Isotropic vs. Anisotropic Chemical Shift Separation | 75 | ||
| 3.1 Introduction | 75 | ||
| 3.2 Theory | 76 | ||
| 3.2.1 MAT and PASS | 76 | ||
| 3.2.2 CSA Amplification | 80 | ||
| 3.3 MAT and PASS Hybrid | 82 | ||
| 3.4 MATPASS of Quadrupolar Nuclei | 86 | ||
| 3.5 CSA Amplification of Uniformly Labeled Systems | 89 | ||
| 3.6 Practical Aspects of MATPASS and xCSA | 92 | ||
| References | 94 | ||
| Methods for Quadrupolar Nuclei | 97 | ||
| Chapter 4 Two-dimensional Methods for Half-integer Quadrupolar Nuclei | 99 | ||
| 4.1 Quadrupolar Nuclei | 99 | ||
| 4.2 High-resolution Methods | 101 | ||
| 4.2.1 MQMAS | 101 | ||
| 4.2.2 Satellite-transition MAS | 110 | ||
| 4.3 Homonuclear Correlations | 113 | ||
| 4.3.1 Double-quantum–Single-quantum Homonuclear Correlations | 113 | ||
| 4.3.2 11B Homonuclear Correlation to Investigate the Structure of Pyrex Glass | 116 | ||
| 4.3.3 27Al DQ–SQ and Dynamic NuclearPolarization to Characterize the Surface of Meso-alumina | 116 | ||
| 4.4 Heteronuclear Correlations | 118 | ||
| 4.4.1 Through-bond Correlations | 118 | ||
| 4.4.2 Through-space Correlations | 123 | ||
| 4.5 More Advanced Techniques | 126 | ||
| 4.6 Conclusion | 130 | ||
| References | 130 | ||
| Chapter 5 14N Solid-state NMR | 134 | ||
| 5.1 Introduction | 134 | ||
| 5.2 Ultra-wideline Methods | 136 | ||
| 5.3 Magic-angle Spinning | 142 | ||
| 5.4 Overtone Spectroscopy | 145 | ||
| 5.5 Indirect Detection | 150 | ||
| 5.6 Dynamic Nuclear Polarisation | 153 | ||
| 5.7 Summary | 156 | ||
| References | 158 | ||
| Characterisation of Dynamics | 161 | ||
| Chapter 6 CODEX-based Methods for Studying Slow Dynamics | 163 | ||
| 6.1 Introduction | 163 | ||
| 6.2 Theory | 165 | ||
| 6.3 Experimental Aspects | 172 | ||
| 6.3.1 Choice of Length of Recoupling Period | 172 | ||
| 6.3.2 Rotor Synchronization | 175 | ||
| 6.3.3 Correction for Losses Due to Relaxation | 176 | ||
| 6.3.4 Spin Diffusion | 177 | ||
| 6.3.5 Relaxation-induced Dipolar Exchange with Recoupling (RIDER) | 179 | ||
| 6.3.6 Effects of Finite Pulse Lengths and Pulse Miss-set | 181 | ||
| 6.4 Examples | 182 | ||
| 6.4.1 Helical Jumps in Semi-crystalline Polymers | 182 | ||
| 6.4.2 Local Motions in Solid Proteins | 187 | ||
| 6.5 Conclusions | 189 | ||
| Acknowledgements | 190 | ||
| References | 190 | ||
| Chapter 7 NMR Studies of Ionic Dynamics in Solids | 193 | ||
| 7.1 Introduction | 193 | ||
| 7.2 General Aspects | 195 | ||
| 7.3 Fast Dynamics | 197 | ||
| 7.3.1 Spin-lattice Relaxation and Field Cycling | 198 | ||
| 7.3.2 Diffusometry Using Magnetic Field Gradients | 202 | ||
| 7.4 Intermediate Dynamics | 203 | ||
| 7.4.1 Spin-lattice Relaxation in the Rotating Frame | 204 | ||
| 7.4.2 One-dimensional Spin-echo Spectra | 207 | ||
| 7.5 Slow Dynamics | 212 | ||
| 7.5.1 Sequences, Cycles and Signals | 212 | ||
| 7.5.2 Selectively Suppressed or Inverted One-dimensional Spectra | 215 | ||
| 7.5.3 Sine-and Cosine-modulated Stimulated-echo Functions | 217 | ||
| 7.5.4 Two-dimensional Exchange Spectroscopy | 220 | ||
| 7.6 Conclusions | 225 | ||
| Acknowledgements | 225 | ||
| References | 225 | ||
| NMR at the Extremes | 231 | ||
| Chapter 8 Low-temperature NMR: Techniques and Applications | 233 | ||
| 8.1 Introduction | 233 | ||
| 8.2 Low-temperature Experimental Techniques and Designs | 234 | ||
| 8.2.1 Cryogenics for Low-temperature NMR | 234 | ||
| 8.2.2 Low-temperature NMR Probes | 236 | ||
| 8.2.3 Low-temperature MAS NMR Probes | 238 | ||
| 8.3 Selected Examples of Low-temperature NMR Studies | 240 | ||
| 8.3.1 Spin Hamiltonian and Dynamics in Fullerides | 241 | ||
| 8.3.2 Probing Novel Quantum Spin States | 245 | ||
| 8.4 Conclusion | 255 | ||
| Acknowledgements | 256 | ||
| References | 256 | ||
| Chapter 9 NMR at High Temperature | 262 | ||
| 9.1 Introduction | 262 | ||
| 9.1.1 Overview | 262 | ||
| 9.1.2 Spectroscopy at High Temperature: Motivations and General Constraints | 263 | ||
| 9.2 Probe Design Considerations | 264 | ||
| 9.2.1 Issues of Signal Intensity | 265 | ||
| 9.2.2 Sample Containers and Heating Methods | 265 | ||
| 9.3 Examples of Applications | 268 | ||
| 9.3.1 Crystalline Solids: Effects of Temperature on Chemical Shifts | 268 | ||
| 9.3.2 Structural Phase Transitions in Solids | 269 | ||
| 9.3.3 Ionic Mobility in Solids | 271 | ||
| 9.3.4 High-temperature Liquids: Chemical Shifts and Average Structure | 274 | ||
| 9.3.5 Relaxation Times and Dynamics in High-temperature Inorganic Liquids | 280 | ||
| 9.3.6 Glass-forming Oxide Liquids: Direct Observations of Species Exchange | 281 | ||
| 9.4 Prognosis | 284 | ||
| Acknowledgements | 285 | ||
| References | 285 | ||
| Methods for Complex Systems | 289 | ||
| Chapter 10 Isotopically Enriched Systems | 291 | ||
| 10.1 Introduction | 291 | ||
| 10.2 Isotope Labelling Techniques for Biomolecules | 292 | ||
| 10.3 Dipolar Recoupling Techniques for Multidimensional NMR Spectroscopy | 299 | ||
| 10.3.1 Zeroth-order Homonuclear Dipolar Recoupling | 300 | ||
| 10.3.2 Second-order Homonuclear Dipolar Recoupling | 303 | ||
| 10.3.3 Heteronuclear Dipolar Recoupling | 310 | ||
| 10.4 Signal Enhancement by DNP | 315 | ||
| 10.5 Conclusion | 318 | ||
| References | 318 | ||
| Chapter 11 NMR Studies of Electrochemical Storage Materials | 322 | ||
| 11.1 Introduction | 322 | ||
| 11.1.1 General Working Principles of Batteries | 323 | ||
| 11.1.2 Anodes | 324 | ||
| 11.1.3 Cathodes | 325 | ||
| 11.1.4 Electrolyte | 326 | ||
| 11.1.5 Beyond Li-ion Technologies? | 327 | ||
| 11.1.6 NMR on Energy Storage Materials | 327 | ||
| 11.2 Methods | 328 | ||
| 11.2.1 Paramagnetic NMR | 328 | ||
| 11.2.2 Calculation of pNMR Parameters | 332 | ||
| 11.2.3 In Situ Solid-state NMR | 337 | ||
| 11.3 Case Studies | 340 | ||
| 11.3.1 Real-time NMR Investigations of Structural Changes in Si Electrodes for LIBs | 340 | ||
| 11.3.2 Mechanistic Insights into Sodium Storage in Hard Carbon from In Situ 23Na NMR | 342 | ||
| 11.3.3 In Situ 23Na NMR Monitoring of Metallic Microstructure Formation in NIBs | 344 | ||
| 11.3.4 TM-substituted LiFePO4: 31P MAS NMR of Multiple TM Disorder Combined with DFT Bond Pathway Decomposition | 345 | ||
| 11.3.5 Paramagnetic Cathode Materials Studied by 17O, 27Al and 25Mg NMR and DFT | 346 | ||
| 11.4 Conclusions and Outlook | 349 | ||
| Acknowledgements | 350 | ||
| References | 350 | ||
| Chapter 12 Disordered Solids | 356 | ||
| 12.1 What Is Disorder? | 356 | ||
| 12.2 Effect of Disorder on the NMR Line Shapes | 358 | ||
| 12.2.1 Spin-1/2 Nuclei | 358 | ||
| 12.2.2 Half-integer Spins: The Czjzek Model | 362 | ||
| 12.3 Specific Acquisition Strategies | 366 | ||
| 12.3.1 Use of Hahn Echoes | 366 | ||
| 12.3.2 DOR, DAS and MQMAS | 371 | ||
| 12.4 Correlation Experiments | 372 | ||
| 12.4.1 Homonuclear Correlations | 373 | ||
| 12.4.2 Heteronuclear Correlations | 378 | ||
| 12.5 Relating NMR Parameters to Local Structure | 381 | ||
| 12.5.1 Semi-empirical Correlation | 381 | ||
| 12.5.2 The Molecular Dynamics/Gauge-includingProjector Augmented-wave (GIPAW) Approach | 382 | ||
| 12.6 Conclusion | 384 | ||
| References | 385 | ||
| Chapter 13 Characterization of Liquid-crystalline Materials by Separated Local Field Methods | 391 | ||
| 13.1 Introduction | 391 | ||
| 13.2 Anisotropic Averaging of Spin Interactions | 393 | ||
| 13.2.1 Heteronuclear Coupling | 393 | ||
| 13.2.2 Chemical Shifts | 394 | ||
| 13.2.3 Quadrupole Coupling | 394 | ||
| 13.3 Experimental Techniques | 395 | ||
| 13.3.1 General Experimental Aspects | 395 | ||
| 13.3.2 Heteronuclear Decoupling | 396 | ||
| 13.3.3 Signal Enhancement of Low-γ Nuclei | 398 | ||
| 13.3.4 Heteronuclear Dipolar NMR Spectroscopy | 398 | ||
| 13.4 SLF NMR in Liquid Crystals | 408 | ||
| 13.4.1 Columnar Mesophases | 410 | ||
| 13.4.2 Twist-bend Nematic Phase | 413 | ||
| 13.4.3 Liquid-crystalline Donor–Acceptor Dyads | 414 | ||
| 13.4.4 Lipids | 414 | ||
| 13.4.5 Hybrid Organic–Inorganic Nanocomposites | 417 | ||
| 13.5 Conclusions | 419 | ||
| Acknowledgements | 420 | ||
| References | 420 | ||
| Subject Index | 424 |